EP0156155A1 - Aqueous dispersions of graft polymers or graft copolymers, their preparation process and their use as water and oil repellent compositions for textile materials - Google Patents
Aqueous dispersions of graft polymers or graft copolymers, their preparation process and their use as water and oil repellent compositions for textile materials Download PDFInfo
- Publication number
- EP0156155A1 EP0156155A1 EP85101728A EP85101728A EP0156155A1 EP 0156155 A1 EP0156155 A1 EP 0156155A1 EP 85101728 A EP85101728 A EP 85101728A EP 85101728 A EP85101728 A EP 85101728A EP 0156155 A1 EP0156155 A1 EP 0156155A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- monomers
- perfluoroalkyl
- dispersions
- ethylenically unsaturated
- graft
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000006185 dispersion Substances 0.000 title claims abstract description 48
- 229920000578 graft copolymer Polymers 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000004753 textile Substances 0.000 title claims abstract description 8
- 239000000203 mixture Substances 0.000 title claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 16
- 239000005871 repellent Substances 0.000 title abstract description 6
- 230000002940 repellent Effects 0.000 title abstract description 6
- 239000000463 material Substances 0.000 title 1
- 239000000178 monomer Substances 0.000 claims abstract description 67
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 21
- 229920003009 polyurethane dispersion Polymers 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000000839 emulsion Substances 0.000 claims description 24
- 229920001228 polyisocyanate Polymers 0.000 claims description 14
- 239000005056 polyisocyanate Substances 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 239000002798 polar solvent Substances 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 41
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- -1 aliphatic radicals Chemical class 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000003995 emulsifying agent Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 230000009965 odorless effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229940052308 general anesthetics halogenated hydrocarbons Drugs 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- PMMZKTPZYZVFAA-UHFFFAOYSA-N 2-(sulfonylamino)acetic acid Chemical compound OC(=O)CN=S(=O)=O PMMZKTPZYZVFAA-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- RTJZWOGSCLVJLD-UHFFFAOYSA-N 2-[1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctylsulfonyl(methyl)amino]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCN(C)S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RTJZWOGSCLVJLD-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000027455 binding Effects 0.000 description 1
- 238000009739 binding Methods 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- PBZROIMXDZTJDF-UHFFFAOYSA-N hepta-1,6-dien-4-one Chemical compound C=CCC(=O)CC=C PBZROIMXDZTJDF-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical class OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 1
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 1
- 235000010269 sulphur dioxide Nutrition 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical class CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 239000003799 water insoluble solvent Substances 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/576—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
Definitions
- the invention relates to aqueous dispersions of graft polymers or copolymers of ethylenically unsaturated perfluoroalkyl monomers which contain aqueous polyurethane dispersions as the graft base, a process for the preparation of these dispersions by polymerization or copolymerization of ethylenically unsaturated perfluoroalkyl monomers and, if appropriate, perfluoroalkyl group-free comonomers and their use in aqueous graft base dispersions as a water repellent and oil repellent for textiles.
- Polymers with perfluoroalkyl groups are suitable substances to make textiles or carpets hydrophobic and oleophobic. These polymers can be used in the form of aqueous emulsions.
- the process of solution polymerization is usually used to prepare corresponding "perfluoroalkyl polymer emulsions", with water-insoluble solvents, for example, usually being used as the reaction medium.
- Methyl isobutyl ketone, halogenated hydrocarbons or acetic acid esters are used which are suitable as solvents for both the monomers and the polymers.
- DE-OS 1 953 345, DE-OS 1 953 348 and DE-OS 1 953 349 describe the preparation of aqueous dispersions of polymers of ethylenically unsaturated monomers in aqueous polyurethane or oligourethane dispersions, but the finding found according to the invention is The producibility of storage-stable dispersions of graft polymers or copolymers of ethylenically unsaturated perfluoroalkyl monomers can also be described as surprising in view of the disclosure of these prior publications, since stable polymers emulsions can also be prepared from the monomers mentioned in the prior publications in other ways, so that it could not be expected that the aforementioned difficulties associated with the production of aqueous dispersions of perfluoroalkyl polymers can be overcome by using aqueous polyurethane dispersions as the graft base.
- the dispersions according to the invention described in more detail below are distinguished from the dispersions of the last-mentioned
- the invention relates to aqueous dispersions of graft polymers or graft copolymers which as Grafting an aqueous, optionally blocked polyisocyanates as a crosslinker dispersed containing polyurethane dispersion and as a graft containing a polymer or a copolymer of ethylenically unsaturated monomers, characterized in that the graft a polymer of ethylenically unsaturated perfluoroalkyl a higher than 367 molecular weight or a copolymer of such P erfluoralkylmonomerer with perfluoroalkyl group-free comonomers.
- the invention also relates to a process for the preparation of these dispersions by polymerization or copolymerization of ethylenically unsaturated monomers or of mixtures of ethylenically unsaturated monomers in aqueous dispersions, optionally containing blocked polyisocyanates as crosslinking agents, with polyurethane dispersions as the graft base, characterized in that ethylenically unsaturated monomers are used ethylenically unsaturated perfluoroalkyl monomers with a molecular weight above 367 or mixtures of such perfluoroalkyl monomers with perfluoroalkyl group-free ethylenically unsaturated monomers in the weight ratio of perfluoroalkyl monomers to perfluoroalkyl group-free monomers of at least 2: 1.
- the invention also relates to the use of these dispersions as hydrophobic and oleophobicizing agents for textiles.
- aqueous dispersions of polyurethanes or polyurethane-polyureas generally have a solids content of 5 to 60, preferably 30 to 50,% by weight.
- Aqueous dispersions of polyurethanes which contain built-in ionic and / or non-ionic hydrophilic centers are particularly suitable.
- Such dispersions and their preparation are described, for example, in US Pat. No. 3,479,310, German Pat. No. 1,495,745, German Pat. No. 1,495,847, US Pat. No. 3,920,598, US Pat. No. 3,905,929, US Pat. No.
- perfluoroalkyl monomers are N-methyl-N-perfluoropentanesulfonamidoethyl methacrylate, N-methyl-perfluorooctanesulfonamidoethyl acrylate, N-methyl-N-perfluorooctanesulfonamidoethyl methacrylate, N-ethyl-N-perfluorooctansulfonamidoethyl methacrylate, N-propyl-oxyl-sulfonamido-methyl-acrylate-N or in the 2-position of the ethyl radical perfluoropentyl, perfluorooctyl or perfluorododecyl-substituted ethyl acrylates or methacrylates.
- Mixtures of the perfluoroalkyl monomers mentioned by way of example can also be used.
- the weight ratio of P is erfluoralkylmonomeren free perfluoroalkyl-to comonomers at least 3: 2, preferably at least 2: 1.
- Suitable such perfluoroalkyl group-free comonomers are, for example, butadiene, isoprene, chloroprene, styrene, ⁇ -methylstyrene, p-methylstyrene, vinyl halides such as vinyl chloride, vinylidene chloride, vinylidene fluoride, vinyl esters such as vinyl acetate, vinyl propionate, vinyl stearate, vinyl methyl ketone, acrylic acid or methacrylic acid, maleic acid ester, maleic acid acid Methacrylic acid esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate or methacrylate, decyl acrylate, lauryl acrylate or methacrylate, stearyl methacrylate, N, N-dimethylaminoethy
- the total amount of ethylenically unsaturated Monomers are dimensioned such that 25 to 900, preferably 50 to 500 parts by weight of the ethylenically unsaturated monomers are available per 100 parts by weight of dispersed polyurethane solid.
- the grafting reaction is usually carried out using the polyurethane dispersion as the graft base, the ethylenically unsaturated perfluoroalkyl monomers and, if appropriate, the perfluoroalkyl group-free comonomers of the initial charge being metered in in liquid form, for example as a monomer mixture, as a solution or as an aqueous emulsion and polymerized onto the graft base with free-radical initiators or be grafted on.
- ketones such as methyl isobutyl ketone
- fatty acid esters such as methyl acetate, ethyl acetate, butyl acetate, ethyl propionate or halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, tetrachloroethane, fluorotrichloromethane, 1,1,2-trifluoromethane-1,2,2-trichloromethane.
- halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, tetrachloroethane, fluorotrichloromethane, 1,1,2-trifluoromethane-1,2,2-trichloromethane.
- Mixtures of the solvents mentioned by way of example can of course also be used.
- the monomers are particularly preferably used in the form of aqueous monomer emulsions, for example by intensive mixing a solution of the monomers in one of the exemplified solvents with water in the presence of suitable emulsifiers of the type exemplified below can be obtained.
- suitable emulsifiers of the type exemplified below can be obtained.
- 10 to 60% by weight solutions or emulsions of the monomers are used to carry out the process according to the invention.
- the (liquid) perfluoroalkyl group-free comonomer which may also be used as a solvent for the perfluoroalkyl monomer.
- the grafting reaction is preferably carried out in the presence of customary free-radical initiators.
- Water-soluble initiators are suitable, e.g. Potassium, sodium or ammonium persulfate or hydrogen peroxide, furthermore redox systems made from persulfate and e.g. Sodium disulfite, sodium hydrogen sulfite or sulfur dioxide.
- Oil-soluble initiators are particularly suitable, e.g. Dibenzoyl peroxide, diacetyl peroxide, dilauroyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroctoate, azoisobutyronitrile, etc.
- grafting activators ie of special substances or monomers with a high transfer activity, which can significantly increase the grafting yields even with a small amount used.
- olefins such as propylene or isobutylene, vinyl chloride, vinyl acetate or triallyl cyanurate.
- regulators such as allylver Bindings or mercaptans for adjusting the molecular weights possible.
- anion-active, cation-active or nonionic emulsifiers can be used to stabilize the dispersions according to the invention and also to prepare the monomer emulsions which are used in the process according to the invention.
- anionic emulsifiers are alkyl sulfonates, alkylarylsulfonates, fatty alcohol sulfates or sulfosuccinic acid esters, furthermore perfluoroalkyl group-containing emulsifiers such as ammonium or tetraethylammonium salts of perfluorooctane sulfonic acid or the potassium salt of N-ethyl-N-perfluorooctane sulfonylglycine.
- cationic emulsifiers are quaternary ammonium or pyridinium salts, e.g. Stearyldimethylbenzylammonium chloride or N, N, N-trimethyl-N-perfluorooctanesulfonamidopropyl-ammonium chloride.
- nonionic emulsifiers are polyglycol ethers, e.g.
- Ethylene oxide / propylene oxide block or copolymers Ethylene oxide / propylene oxide block or copolymers, alkoxylation products, in particular ethoxylation products of fatty alcohols, alkylphenols, fatty acids, fatty acid amides, sorbitan monooleate or of N-alkyl-N-perfluorooctanesulfonylglycine.
- alkoxylation products in particular ethoxylation products of fatty alcohols, alkylphenols, fatty acids, fatty acid amides, sorbitan monooleate or of N-alkyl-N-perfluorooctanesulfonylglycine.
- Combinations of nonionic emulsifiers with anion-active or cation-active emulsifiers of the type mentioned by way of example are particularly suitable.
- the process according to the invention is generally at from 20 to 120 ° C., preferably from 50 to 100 ° C. temperatures if necessary carried out under an intergas atmosphere (nitrogen) and optionally under pressure, the monomers and the auxiliaries and additives being incorporated into the submitted polyurethane dispersion with constant mixing. Because of the excellent stability of the dispersions according to the invention, it is readily possible to remove solvents or volatile residual monomers by degassing in conventional distillation apparatuses, such as, for example, rotary evaporators or thin layers, without coagulation occurring as in the case of conventional known emulsions of perfluoroalkyl polymers. After degassing, odorless dispersions are obtained which have a long shelf life.
- the solids content of the dispersions according to the invention is generally 5 to 50, preferably 10 to 30,% by weight, depending on the concentration of the polyurethane dispersion provided and the amount of water (and, if appropriate, solvent not removed) introduced with the monomers.
- the fluorine content in the solid is generally 6 to 50, preferably 10 to 30,% by weight.
- Films can be produced from the dispersions according to the invention which have excellent hydrophobicity and oleophobicity.
- the dispersions are excellent as impregnation agents to make textiles made of natural and synthetic fibers, carpets, paper and leather oil and water repellent.
- Dispersions according to the invention which contain blocked polyisocyanates in dispersed form can be processed into particularly high-quality crosslinked coatings by briefly heating the coatings produced with them to temperatures above 100.degree.
- a homogeneous, clear mixture is produced at 60 ° C. from the polyester, which is dewatered at 100 ° C. in vacuo, the N-methylpyrrolidone, the trimethylolpropane, the dimethylolpropionic acid and the triethylamine.
- the diisocyanate is then added and the mixture is stirred at 80 ° C. for about 2 hours until a (corrected) NCO value of 2.6% is reached.
- the mixture is cooled to 60 ° C. and the acetonazine is added to the prepolymer obtained. Allow to stir well then run in the water. The fine-particle dispersion that forms is stirred at 70 ° C. for 5 hours.
- the solids content is 40% and the Ford cup viscosity (4 mm nozzle) 30 seconds.
- a homogeneous, clear mixture is produced at 60 ° C. from the polyester, which is dewatered at 100 ° C. in vacuo, the N-methylpyrrolidone, the dimethylolpropionic acid and the triethylamine.
- the diisocyanate is then added and the mixture is stirred at 80 ° C. for 2 to 3 hours until a (corrected) 2) N CO value of 2.3% is reached.
- the mixture is cooled to 60 ° C. and the blocked polyisocyanate 1 ) and the acetonazine are added in succession to the prepolymer obtained.
- the water is then run in with thorough stirring, whereupon a finely divided dispersion forms, which is finally stirred at 70 ° C. for 5 hours.
- a monomer emulsion 3 is prepared by mixing solutions 1 and 2 with the aid of an ultrasound disperser, which is used for the subsequent grafting reaction.
- the mixture is then stirred at 75 ° C. for 1 h, diluted with 200 g of deionized water and a stable dispersion is obtained without solid precipitation.
- a monomer emulsion 3 is prepared by mixing solutions 1 and 2 using a high-speed mixer, which is used for the following grafting reaction:
- 300 g of polyurethane dispersion B are introduced as a template into a stirred flask and heated to 75 ° C. under N 2 .
- 600 g of monomer emulsion 3 and a solution of 5.0 g of dilauroyl peroxide in 100 g of methyl isobutyl ketone are metered in uniformly over the course of 2 hours.
- the mixture is then stirred at 75 ° C. for 1 h, diluted with 400 g of deionized water and a stable dispersion is obtained without solid precipitation.
- the dispersion can be degassed on a rotary evaporator at 60 ° C and 200 mbar by removing about 400 g of distillate. 1000 g of a stable, almost odorless dispersion are obtained with the following analysis data:
- a mono-emulsion 3 is prepared which is used for the subsequent grafting reaction.
- 300 g of polyurethane dispersion A are introduced into a stirred flask and heated to 75 ° C. under N 2 .
- 900 g of monomer emulsion 3 and a solution of 6.0 g of dilauroyl peroxide in 100 g of ethyl acetate are metered in uniformly at 75 ° C. in the course of 2 hours.
- a monomer emulsion 3 is prepared by mixing solutions 1 and 2 using an ultrasound disperser, which is used for the following grafting reaction:
- 300 g of polyurethane dispersion A are introduced into a stirred flask and heated to 75 ° C. under N 2 .
- 600 g of monomer emulsion 3 and a solution of 6.0 g of dilauroyl peroxide in 100 g of methyl isobutyl ketone are metered in uniformly over the course of 3 hours.
- 300 g of polyurethane dispersion A are introduced into a stirred flask and heated to 75 ° C. under N 2 .
- 600 g of monomer emulsion 3 and a solution of 5.0 g of dilauroyl peroxide in 80 g of methyl isobutyl ketone are metered in uniformly within 3 hours.
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- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Graft Or Block Polymers (AREA)
- Polymerisation Methods In General (AREA)
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- Paints Or Removers (AREA)
Abstract
Wäßrige Dispersionen von Pfropfpolymerisaten oder Pfropfcopolymerisaten, die als Pfropfgrundlage eine wäßrige Polyurethandispersion und als Pfropfauflage ein Polymerisat oder ein Copolymerisat aus ethylenisch ungesättigten Perfluoralkylmonomeren und gegebenenfalls Perfluoralkylgruppen- freien Comonomeren enthalten, ein Verfahren zur Herstellung dieser Dispersionen durch Polymerisation oder Copolymerisation der genannten Monomeren in wäßrigen Polyurethandispersion als Pfropfgrundlage und die Verwendung der Dispersionen als Hydrophobierungs- und Oleophobierungsmittel für Textilien bzw. zur Herstellung von Überzügen.Aqueous dispersions of graft polymers or graft copolymers which contain an aqueous polyurethane dispersion as the graft base and a polymer or a copolymer of ethylenically unsaturated perfluoroalkyl monomers and optionally perfluoroalkyl group-free comonomers as a graft base, a process for the preparation of these dispersions by polymerization or copolymerization of the monomers mentioned as polymerization Graft base and the use of the dispersions as water repellents and oil repellents for textiles or for the production of coatings.
Description
Die Erfindung betrifft wäßrige Dispersionen von Pfropfpolymerisaten oder -copolymerisaten von ethylenisch ungesättigten Perfluoralkylmonomeren, die als Pfropfgrundlage wäßrige Polyurethandispersionen enthalten, ein Verfahren zur Herstellung dieser Dispersionen durch Polymerisation oder Copolymerisation von ethylenisch ungesättigten Perfluoralkylmonomeren und gegebenenfalls Perfluoralkylgruppen-freien Comonomeren in wäßrigen Polyurethandispersionen als Pfropfgrundlage und ihre Verwendung als Hydrophobierungs- und Oleophobierungsmittel für Textilien.The invention relates to aqueous dispersions of graft polymers or copolymers of ethylenically unsaturated perfluoroalkyl monomers which contain aqueous polyurethane dispersions as the graft base, a process for the preparation of these dispersions by polymerization or copolymerization of ethylenically unsaturated perfluoroalkyl monomers and, if appropriate, perfluoroalkyl group-free comonomers and their use in aqueous graft base dispersions as a water repellent and oil repellent for textiles.
Polymere mit Perfluoralkylgruppen sind geeignete Substanzen, um Textilien oder Teppiche hydrophob und oleophob auszurüsten. Diese Polymere können in Form von wäßrigen Emulsionen eingesetzt werden.Polymers with perfluoroalkyl groups are suitable substances to make textiles or carpets hydrophobic and oleophobic. These polymers can be used in the form of aqueous emulsions.
Die Herstellung wäßriger Emulsionen nach bekannten Verfahrensweisen der Emulsionspolymerisation ist jedoch schwierig, da ethylenisch ungesättigte Perfluoralkylmonomere extrem wasserunlöslich sind und in Wasser keine stabilen Emulsionen erhalten werden können.However, the preparation of aqueous emulsions according to known methods of emulsion polymerization is difficult since ethylenically unsaturated perfluoroalkyl monomers are extremely water-insoluble and no stable emulsions can be obtained in water.
In US-PS 3 403 122 ist ein Verfahren beschrieben, Perfluoralkylpolymere in wäßrigen Medien, die zur Erhöhung der Monomerlöslichkeit 5 bis 50 % an wasserlöslichen, organischen Substanzen z.B. Aceton oder Methanol enthalten, nach der Verfahrensweise der Emulsionspolymerisation herzustellen. Man erhält jedoch auf diese Weise grobe und wenig lagerstabile Dispersionen. Zudem sind wasserlösliche, organische Solventien wie Aceton oder Methanol Fällmittel für viele Polymere, so daß dieses Verfahren bei vielen der üblicherweise eingesetzten Copolymerisationssystemen nicht angewendet werden kann.In U.S. Patent 3,403,122 a process is described, perfluoroalkyl polymers in aqueous media, which increase the monomer solubility 5 to 50% of water-soluble organic substances e.g. Contain acetone or methanol, according to the procedure of emulsion polymerization. However, coarse dispersions which are not very stable in storage are obtained in this way. In addition, water-soluble organic solvents such as acetone or methanol are precipitants for many polymers, so that this process cannot be used in many of the copolymerization systems that are commonly used.
Die US-PS 3 068 187 beschreibt segmentierte Copolymere d.h. Block- oder Pfropfcopolymere von ethylenisch ungesättigten Perfluoralkylmonomeren mit ethylenisch ungesättigten Monomeren, die weniger als 10 % Fluor enthalten, sowie ihre Herstellung nach der Verfahrensweise der Emulsionspolymerisation, wobei das weniger als 10 % Fluor enthaltende Monomer, z.B. Butadien oder Chloropren in wäßriger Emulsion vorpolymerisiert wird und anschließend oder gleichzeitig das Perfluoralkylmonomer auf diese Voremulsion aufpolymerisiert wird. Jedoch ist auch in diesen Fällen der Zusatz von wasserlöslichen Solventien wie Aceton oder Methanol erforderlich, wodurch die Stabilität der erhaltenen Emulsion herabgesetzt wird oder sogar vollständige Koagulation eintritt.US Pat. No. 3,068,187 describes segmented copolymers, ie block or graft copolymers of ethylenically unsaturated perfluoroalkyl monomers with ethylenically unsaturated monomers which contain less than 10% fluorine, and their preparation by the procedure of emulsion polymerization, the monomer containing less than 10% fluorine , for example butadiene or chloroprene is prepolymerized in an aqueous emulsion and then or at the same time the perfluoroalkyl monomer is polymerized onto this pre-emulsion. However in these cases, too, the addition of water-soluble solvents such as acetone or methanol is necessary, which reduces the stability of the emulsion obtained or even causes complete coagulation.
Um diese Nachteile zu vermeiden, wird zur Herstellung von entsprechenden "Perfluoralkylpolymerisatemulsionen" meist das Verfahren der Lösungspolymerisation angewendet, wobei als Reaktionsmedium üblicherweise wasserunlösliche Solventien z.B. Methylisobutylketon, Halogenkohlenwasserstoffe oder Essigsäureester dienen, die als Lösungsmittel sowohl für die Monomeren als auch für die Polymeren geeignet sind. Durch Emulgierung dieser Polymerlösung in Wasser mit Hilfe spezieller Emulgieraggregate oder Homogenisatoren ist es meist möglich, genügend feinteilige und lagerstabile Dispersionen zu gewinnen. Dieses Verfahren ist jedoch durch die notwendige weitere Verfahrensstufe der Emulgierung umständlich und aufwendig, so daß weiterhin der Wunsch nach einer technisch einfacheren Verfahrensweise der Emulsionspolymerisation besteht.In order to avoid these disadvantages, the process of solution polymerization is usually used to prepare corresponding "perfluoroalkyl polymer emulsions", with water-insoluble solvents, for example, usually being used as the reaction medium. Methyl isobutyl ketone, halogenated hydrocarbons or acetic acid esters are used which are suitable as solvents for both the monomers and the polymers. By emulsifying this polymer solution in water with the aid of special emulsifying units or homogenizers, it is usually possible to obtain sufficiently fine-particle dispersions that are stable in storage. However, this process is cumbersome and time-consuming due to the necessary further process step of emulsification, so that there is still a desire for a technically simpler procedure for emulsion polymerization.
Es wurde nun gefunden, daß man lagerstabile, hydrophobierend und oleophobierend wirkende Dispersionen erhalten kann, wenn man in Gegenwart von wäßrigen Polyurethandispersionen die nachstehend näher beschriebenen ethylenisch ungesättigten Perfluoralkylmonomeren, vorzugsweise in Kombination mit weiteren Vinylmonomeren nach der Verfahrensweise einer Pfropfpolymerisation polymerisiert. Unabhängig von der Pfropfausbeute wird die Gesamtmenge an polymerisierten Monomeren als "Pfropfauflage" bezeichnet.It has now been found that storage-stable, hydrophobic and oleophobic dispersions can be obtained if the ethylenically unsaturated perfluoroalkyl monomers described in more detail below, preferably in combination with other vinyl monomers, are polymerized in the presence of aqueous polyurethane dispersions by the procedure of a graft polymerization. Regardless of the graft yield the total amount of polymerized monomers referred to as "graft".
In DE-OS 1 953 345, DE-OS 1 953 348 und DE-OS 1 953 349 wird zwar schon die Herstellung von wäßrigen Dispersionen von Polymerisaten ethylenisch ungesättigter Monomerer in wäßrigem Polyurethan- bzw. Oligourethandispersionen beschrieben, jedoch ist der erfindungsgemäß aufgefundene Befund der Herstellbarkeit von lagerstabilen Dispersionen von Pfropfpolymerisaten oder -copolymerisaten ethylenisch ungesättigter Perfluoralkylmonomerer auch im Hinblick auf die Offenbarung dieser Vorveröffentlichungen als überraschend zu bezeichnen, da aus den in den Vorveröffentlichungen genannten Monomeren auch auf anderem Wege stabile Polymerisatemulsionen herstellbar sind, so daß nicht erwartet werden konnte, daß die genannten, mit der Herstellung von wäßrigen Dispersionen von Perfluoralkylpolymeren zusammenhängenden Schwierigkeiten durch die Verwendung von wäßrigen Polyurethandispersionen als Pfropfgrundlage überwunden werden können. Die nachstehend näher beschriebenen erfindungsgemäßen Dispersionen zeichnen sich im übrigen gegenüber den Dispersionen der zuletzt genannten Vorveröffentlichungen dadurch aus, daß sie hervorragende Oleophobierungsmittel für Textilien darstellen.DE-OS 1 953 345, DE-OS 1 953 348 and DE-OS 1 953 349 describe the preparation of aqueous dispersions of polymers of ethylenically unsaturated monomers in aqueous polyurethane or oligourethane dispersions, but the finding found according to the invention is The producibility of storage-stable dispersions of graft polymers or copolymers of ethylenically unsaturated perfluoroalkyl monomers can also be described as surprising in view of the disclosure of these prior publications, since stable polymers emulsions can also be prepared from the monomers mentioned in the prior publications in other ways, so that it could not be expected that the aforementioned difficulties associated with the production of aqueous dispersions of perfluoroalkyl polymers can be overcome by using aqueous polyurethane dispersions as the graft base. The dispersions according to the invention described in more detail below are distinguished from the dispersions of the last-mentioned prior publications in that they are excellent oleophobicizing agents for textiles.
Gegenstand der Erfindung sind wäßrige Dispersionen von Pfropfpolymerisaten oder Pfropfcopolymerisaten, die als Pfropfgrundlage eine wäßrige, gegebenenfalls blockierte Polyisocyanate als Vernetzer dispergiert enthaltende, Polyurethandispersion und als Pfropfauflage ein Polymerisat oder ein Copolymerisat aus ethylenisch ungesättigten Monomeren enthalten, dadurch gekennzeichnet, daß die Pfropfauflage ein Polymerisat aus ethylenisch ungesättigten Perfluoralkylmonomeren eines über 367 liegenden Molekulargewichts oder ein Copolymerisat derartiger Perfluoralkylmonomerer mit Perfluoralkylgruppen-freien Comonomeren darstellt.The invention relates to aqueous dispersions of graft polymers or graft copolymers which as Grafting an aqueous, optionally blocked polyisocyanates as a crosslinker dispersed containing polyurethane dispersion and as a graft containing a polymer or a copolymer of ethylenically unsaturated monomers, characterized in that the graft a polymer of ethylenically unsaturated perfluoroalkyl a higher than 367 molecular weight or a copolymer of such P erfluoralkylmonomerer with perfluoroalkyl group-free comonomers.
Gegenstand der Erfindung ist auch ein Verfahren zur Herstellung dieser Dispersionen durch Polymerisation oder Copolymerisation von ethylenisch ungesättigten Monomeren oder von Gemischen von ethylenisch ungesättigten Monomeren in wäßrigen, gegebenenfalls blockierte Polyisocyanate als Vernetzer dispergiert enthaltenden, Polyurethandispersionen als Pfropfgrundlage, dadurch gekennzeichnet, daß man als ethylenisch ungesättigte Monomere ethylenisch ungesättigte Perfluoralkylmonomere eines über 367 liegenden Molekulargewichts oder Gemische derartiger Perfluoralkylmonomerer mit Perfluoralkylgruppen-freien ethylenisch ungesättigten Monomeren im Gewichtsverhältnis von Perfluoralkylmonomeren zu Perfluoralkylgruppen-freien Monomeren von mindestens 2:1 verwendet.The invention also relates to a process for the preparation of these dispersions by polymerization or copolymerization of ethylenically unsaturated monomers or of mixtures of ethylenically unsaturated monomers in aqueous dispersions, optionally containing blocked polyisocyanates as crosslinking agents, with polyurethane dispersions as the graft base, characterized in that ethylenically unsaturated monomers are used ethylenically unsaturated perfluoroalkyl monomers with a molecular weight above 367 or mixtures of such perfluoroalkyl monomers with perfluoroalkyl group-free ethylenically unsaturated monomers in the weight ratio of perfluoroalkyl monomers to perfluoroalkyl group-free monomers of at least 2: 1.
Gegenstand der Erfindung ist auch die Verwendung dieser Dispersionen als Hydrophobierungs- und Oleophobierungsmittel für Textilien.The invention also relates to the use of these dispersions as hydrophobic and oleophobicizing agents for textiles.
Für das erfindungsgemäße Verfahren als Pfropfgrundlage geeignete wäßrige Polyurethandispersionen sind alle beliebigen wäßrigen Dispersionen von Polyurethanen bzw. von Polyurethan-Polyharnstoffen. Diese Dispersionen weisen im allgemeinen einen Feststoffgehalt von 5 bis 60, vorzugsweise 30 bis 50 Gew.-% auf. Besonders gut geeignet sind wäßrige Dispersionen von Polyurethanen, die eingebaute ionische und/oder nicht-ionische hydrophile Zentren enthalten. Derartige Dispersionen bzw. ihre Herstellung sind z.B. in US-PS 3 479 310, DE-PS 1 495 745, DE-AS 1 495 847, US-PS 3 920 598, US-PS 3 905 929, US-PS 4 108 814, US-PS 4 092 286, US-PS 4 190 566, US-PS 4 237 264, US-PS 4 238 378, DE-OS 2 725 589, DE-US 2 732 131, DE-OS 2 811 148, US-PS 4 269 748, US-PS 4 292 226 oder DE-OS 3 137 748 beschrieben. Besonders hochwertige erfindungsgemäße Dispersionen werden dann erhalten, wenn als Pfropfgrundlage wäßrige Polyurethandispersionen eingesetzt werden, die blockierte Polyisocyanate als Vernetzer dispergiert enthalten. Die Herstellung derartiger Polyurethandispersionen ist in der letztgenannten DE-OS 3 137 748 offenbart.Are olyurethandispersionen as graft suitable aqueous P for the inventive method any and all aqueous dispersions of polyurethanes or polyurethane-polyureas. These dispersions generally have a solids content of 5 to 60, preferably 30 to 50,% by weight. Aqueous dispersions of polyurethanes which contain built-in ionic and / or non-ionic hydrophilic centers are particularly suitable. Such dispersions and their preparation are described, for example, in US Pat. No. 3,479,310, German Pat. No. 1,495,745, German Pat. No. 1,495,847, US Pat. No. 3,920,598, US Pat. No. 3,905,929, US Pat. No. 4,108,814 , US-PS 4 092 286, US-PS 4 190 566, US-PS 4 237 264, US-PS 4 238 378, DE-OS 2 725 589, DE-US 2 732 131, DE-OS 2 811 148, U.S. Patent 4,269,748, U.S. Patent 4,292,226, or DE-OS 3 137 748. Particularly high-quality dispersions according to the invention are obtained if aqueous polyurethane dispersions which contain blocked polyisocyanates as dispersing agents are used as the graft base. The preparation of such polyurethane dispersions is disclosed in the last-mentioned DE-OS 3 137 748.
Bei den erfindungswesentlichen, ethylenisch ungesättigten Perfluoralkylmonomeren handelt es sich um beliebige ethylenisch ungesättigte Verbindungen, die mindestens fünf perfluorierte Kohlenstoffatome in Form von Perfluoralkylgruppen aufweisen, wobei unter "Perfluoralkylgruppen" gesättigte, perfluorierte, aliphatische Radikale zu verstehen sind, die eine lineare, verzweigte oder auch cyclische Struktur aufweisen können. Die geeigneten Perfluoralkylmonomeren weisen ein über 367 liegendes, d.h. bei mindestens 368 liegendes Molekulargewicht auf. Geeignete derartige Perfluoralkylmonomere sind insbesondere Acrylate oder Methacrylate der allgemeinen Formeln
- R für Wasserstoff oder eine Methylgruppe steht,
- R' für Wasserstoff oder eine Alkylgruppe mit 1 bis 6 Kohlenstoffatomen steht und
- n für 5 oder eine ganze Zahl größer als 5, vorzugsweise 5 bis 12 steht.
- R represents hydrogen or a methyl group,
- R 'represents hydrogen or an alkyl group having 1 to 6 carbon atoms and
- n represents 5 or an integer greater than 5, preferably 5 to 12.
Beispiele derartiger Perfluoralkylmonomerer sind N-Methyl-N-perfluorpentansulfonamidoethylmethacrylat, N-Methyl-perfluoroctansulfonamidoethylacrylat, N-Methyl-N-perfluoroctansulfonamidoethylmethacrylat, N-Ethyl-N-perfluoroctansulfonamidoethylmethacrylat, N-Propyl-N-perfluoroctansulfonamidoethylacrylat, N-Hexyl-N-perfluordodecansulfonamidoethylacrylat, oder in 2-Stellung des Ethylrests Perfluorpentyl-, Perfluoroctyl- oder Perfluordodecyl-substituierte Ethylacrylate bzw. -methacrylate. Selbstverständlich können auch Mischungen der beispielhaft genannten Perfluoralkylmonomereren eingesetzt werden.Examples of such perfluoroalkyl monomers are N-methyl-N-perfluoropentanesulfonamidoethyl methacrylate, N-methyl-perfluorooctanesulfonamidoethyl acrylate, N-methyl-N-perfluorooctanesulfonamidoethyl methacrylate, N-ethyl-N-perfluorooctansulfonamidoethyl methacrylate, N-propyl-oxyl-sulfonamido-methyl-acrylate-N or in the 2-position of the ethyl radical perfluoropentyl, perfluorooctyl or perfluorododecyl-substituted ethyl acrylates or methacrylates. Of course Mixtures of the perfluoroalkyl monomers mentioned by way of example can also be used.
Neben den beispielhaft genannten Perfluoralkylmonomeren können auch weitere, Perfluoralkylgruppen-freie Comonomere mitverwendet werden. Falls derartige Comonomere mitverwendet werden, liegt das Gewichtsverhältnis von Perfluoralkylmonomeren zu Perfluoralkylgruppen-freien Comonomeren bei mindestens 3:2, vorzugsweise bei mindestens 2:1.In addition to the perfluoroalkyl monomers mentioned by way of example, further comonomers free of perfluoroalkyl groups can also be used. If such comonomers are used, the weight ratio of P is erfluoralkylmonomeren free perfluoroalkyl-to comonomers at least 3: 2, preferably at least 2: 1.
Geeignete derartige Perfluoralkylgruppen-freie Comonomere sind beispielsweise Butadien, Isopren, Chloropren, Styrol, α-Methylstyrol, p-Methylstyrol, Vinylhalogenide wie Vinylchlorid, Vinylidenchlorid, Vinylidenfluorid, Vinylester wie Vinylacetat, Vinylpropionat, Vinylstearat, Vinylmethylketon, Acrylsäure, Methacrylsäure, Maleinsäureanhydrid, Acrylsäureester oder Methacrylsäureester wie Methylacrylat, Methylmethacrylat, Ethylacrylat, Ethylmethacrylat, Propylacrylat, Butylacrylat, 2-Ethylhexylacrylat oder -methacrylat, Decylacrylat, Laurylacrylat oder -methacrylat, Stearylmethacrylat, N,N-Dimethylaminoethylmethacrylat, 2-Hydroxyethylmethacrylat, 2-Hydroxypropylmethacrylat, Glycidylmethacrylat, Acrylamid, Methacrylamid, N-Methylolacrylamid, Acrylnitril, Methacrylnitril oder N-substituierte Maleinimide. Geeignet sind auch Mischungen dieser Comonomeren.Suitable such perfluoroalkyl group-free comonomers are, for example, butadiene, isoprene, chloroprene, styrene, α-methylstyrene, p-methylstyrene, vinyl halides such as vinyl chloride, vinylidene chloride, vinylidene fluoride, vinyl esters such as vinyl acetate, vinyl propionate, vinyl stearate, vinyl methyl ketone, acrylic acid or methacrylic acid, maleic acid ester, maleic acid acid Methacrylic acid esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate or methacrylate, decyl acrylate, lauryl acrylate or methacrylate, stearyl methacrylate, N, N-dimethylaminoethyl methacrylate, acrylate, methacrylate, methacrylate, methacrylate, methacrylate, N-methylolacrylamide, acrylonitrile, methacrylonitrile or N-substituted maleimides. Mixtures of these comonomers are also suitable.
Bei der Durchführung des erfindungsgemäßen Verfahrens wird die Gesamtmenge der ethylenisch ungesättigten Monomeren so bemessen, daß pro 100 Gew.-Teilen dispergiertem Polyurethanfeststoff 25 bis 900, vorzugsweise 50 bis 500 Gew.-Teile der ethylenisch ungesättigten Monomeren zur Verfügung stehen.When carrying out the process according to the invention, the total amount of ethylenically unsaturated Monomers are dimensioned such that 25 to 900, preferably 50 to 500 parts by weight of the ethylenically unsaturated monomers are available per 100 parts by weight of dispersed polyurethane solid.
Die Pfropfreaktion wird üblicherweise unter Vorlage der Polyurethandispersion als Pfropfgrundlage durchgeführt, wobei die ethylenisch ungesättigten Perfluoralkylmonomeren sowie gegebenenfalls die Perfluoralkylgruppen-freien Comonomeren der Vorlage in flüssiger Form, z.B. als Monomerengemisch, als Lösung oder als wäßrige Emulsion zudosiert werden und mit radikalischen Initiatoren auf die Pfropfgrundlage aufpolymerisiert bzw. aufgepfropft werden. Zur Bereitung der Lösung oder der wäßrigen Emulsion werden bevorzugt in Wasser schwerlösliche oder unlösliche, vorzugsweise polare Lösungsmittel eingesetzt, die jedoch als Lösungsmittel für die Perfluoralkylmonomeren sowie die gegebenenfalls verwendeten Perfluoralkylgruppen-freien Comonomeren geeignet sind. Beispiele sind Ketone wie Methylisobutylketon, Fettsäureester wie Essigsäuremethylester, Essigsäureethylester, Essigsäurebutylester, Propionsäureethylester oder Halogenkohlenwasserstoffe wie Methylenchlorid, Chloroform, Tetrachlorkohlenstoff, Tetrachlorethan, Fluortrichlormethan, 1,1,2-Trifluor-1,2,2-trichlorethan. Gemische der beispielhaft genannten Lösungsmittel können selbstverständlich ebenfalls verwendet werden. Besonders bevorzugt gelangen die Monomeren in Form von wäßrigen Monomeremulsionen zum Einsatz, die beispielsweise durch intensives Vermischen einer Lösung der Monomeren in einem der beispielhaft genannten Lösungsmittel mit Wasser in Gegenwart geeigneter Emulgatoren der nachstehend beispielhaft genannten Art erhalten werden können. Im allgemeinen kommen bei der Durchführung des erfindungsgemäßen Verfahrens 10 bis 60-gew.-%ige Lösungen oder Emulsionen der Monomeren zum Einsatz. Es ist natürlich ebenfalls möglich, das gegebenenfalls mitverwendete (flüssige) Perfluoralkylgruppen-freie Comonomere als Lösungsmittel für das Perfluoralkylmonomere zu benutzen.The grafting reaction is usually carried out using the polyurethane dispersion as the graft base, the ethylenically unsaturated perfluoroalkyl monomers and, if appropriate, the perfluoroalkyl group-free comonomers of the initial charge being metered in in liquid form, for example as a monomer mixture, as a solution or as an aqueous emulsion and polymerized onto the graft base with free-radical initiators or be grafted on. To prepare the solution or the aqueous emulsion it is preferred to use sparingly soluble or insoluble, preferably polar, solvents in water, but these are suitable as solvents for the perfluoroalkyl monomers and the optionally used perfluoroalkyl group-free comonomers. Examples are ketones such as methyl isobutyl ketone, fatty acid esters such as methyl acetate, ethyl acetate, butyl acetate, ethyl propionate or halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, tetrachloroethane, fluorotrichloromethane, 1,1,2-trifluoromethane-1,2,2-trichloromethane. Mixtures of the solvents mentioned by way of example can of course also be used. The monomers are particularly preferably used in the form of aqueous monomer emulsions, for example by intensive mixing a solution of the monomers in one of the exemplified solvents with water in the presence of suitable emulsifiers of the type exemplified below can be obtained. In general, 10 to 60% by weight solutions or emulsions of the monomers are used to carry out the process according to the invention. It is of course also possible to use the (liquid) perfluoroalkyl group-free comonomer which may also be used as a solvent for the perfluoroalkyl monomer.
Die Pfropfreaktion wird vorzugsweise in Gegenwart von üblichen radikalbildenden Initiatoren durchgeführt. Geeignet sind wasserlösliche Initiatoren, z.B. Kalium-, Natrium- oder Ammoniumpersulfat oder Wasserstoffperoxid, weiterhin Redoxsysteme aus Persulfat und z.B. Natriumdisulfit, Natriumhydrogensulfit oder Schwefeldioxid. Besonders geeignet sind öllösliche Initiatoren z.B. Dibenzoylperoxid, Diacetylperoxid, Dilauroylperoxid, Di-tert.-butylperoxid, tert.-Butylhydroperoxid, Cumolhydroperoxid, tert.-Butylperoctoat, Azoisobuttersäuredinitril usw.The grafting reaction is preferably carried out in the presence of customary free-radical initiators. Water-soluble initiators are suitable, e.g. Potassium, sodium or ammonium persulfate or hydrogen peroxide, furthermore redox systems made from persulfate and e.g. Sodium disulfite, sodium hydrogen sulfite or sulfur dioxide. Oil-soluble initiators are particularly suitable, e.g. Dibenzoyl peroxide, diacetyl peroxide, dilauroyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroctoate, azoisobutyronitrile, etc.
Zur Verbesserung der Pfropfausbeuten ist der Einsatz sogenannter Pfropfaktivatoren möglich, d.h. von speziellen Substanzen oder Monomeren mit einer hohen Übertragungsaktivität, die bereits bei geringer Einsatzmenge die Pfropfausbeuten wesentlich erhöhen können. Beispiele sind Olefine wie Propylen oder Isobutylen, Vinylchlorid, Vinylacetat oder Triallylcyanurat. Ebenso ist die Verwendung von sogenannten Reglern, wie z.B. Allylverbindungen oder Mercaptanen zur Einstellung der Molekulargewichte möglich.To improve the grafting yields, the use of so-called grafting activators is possible, ie of special substances or monomers with a high transfer activity, which can significantly increase the grafting yields even with a small amount used. Examples are olefins such as propylene or isobutylene, vinyl chloride, vinyl acetate or triallyl cyanurate. Likewise, the use of so-called regulators, such as allylver Bindings or mercaptans for adjusting the molecular weights possible.
Zur Stabilisierung der erfindungsgemäßen Dispersionen und auch zur Herstellung der Monomeremulsionen, die beim erfindungsgemäßen Verfahren eingesetzt werden, können übliche anionenaktive, kationenaktive oder nichtionogene Emulgatoren eingesetzt werden. Beispiele für anionenaktive Emulgatoren sind Alkylsulfonate, Alkylarylsulfonate, Fettalkoholsulfate oder Sulfobernsteinsäureester, ferner Perfluoralkylgruppen-enthaltende Emulgatoren wie Ammonium- oder Tetraethylammoniumsalze der Perfluoroctansulfonsäure oder das Kaliumsalz des N-Ethyl-N-perfluoroctansulfonylglycins. Beispiele für kationenaktive Emulgatoren sind quartäre Ammonium-oder Pyridiniumsalze, z.B. Stearyldimethylbenzylammoniumchlorid oder N,N,N-Trimethyl-N-perfluoroctan- sulfonamidopropyl-ammoniumchlorid. Beispiele für nichtionogene Emulgatoren sind Polyglykolether, z.B. Ethylenoxid/Propylenoxid-Block- oder -Copolymere, Alkoxylierungsprodukte, insbesondere Ethoxylierungsprodukte von Fettalkoholen, Alkylphenolen, Fettsäuren, Fettsäureamiden, Sorbitanmonooleat oder von N-Alkyl-N-perfluoroctansulfonylglycin. Besonders geeignet sind Kombinationen von nichtionogenen Emulgatoren mit anionenaktiven oder kationenaktiven Emulgatoren der beispielhaft genannten Art.Conventional anion-active, cation-active or nonionic emulsifiers can be used to stabilize the dispersions according to the invention and also to prepare the monomer emulsions which are used in the process according to the invention. Examples of anionic emulsifiers are alkyl sulfonates, alkylarylsulfonates, fatty alcohol sulfates or sulfosuccinic acid esters, furthermore perfluoroalkyl group-containing emulsifiers such as ammonium or tetraethylammonium salts of perfluorooctane sulfonic acid or the potassium salt of N-ethyl-N-perfluorooctane sulfonylglycine. Examples of cationic emulsifiers are quaternary ammonium or pyridinium salts, e.g. Stearyldimethylbenzylammonium chloride or N, N, N-trimethyl-N-perfluorooctanesulfonamidopropyl-ammonium chloride. Examples of nonionic emulsifiers are polyglycol ethers, e.g. Ethylene oxide / propylene oxide block or copolymers, alkoxylation products, in particular ethoxylation products of fatty alcohols, alkylphenols, fatty acids, fatty acid amides, sorbitan monooleate or of N-alkyl-N-perfluorooctanesulfonylglycine. Combinations of nonionic emulsifiers with anion-active or cation-active emulsifiers of the type mentioned by way of example are particularly suitable.
Das erfindungsgemäße Verfahren wird im allgemeinen bei 20 bis 120°C, vorzugsweise 50 bis 100°C liegenden Temperaturen gegebenenfalls unter Intergasatmosphäre (Stickstoff) und gegebenenfalls unter Druck durchgeführt, wobei die Monomeren und die Hilfs- und Zusatzmittel der vorgelegten Polyurethandispersion unter ständigem Durchmischen einverleibt werden. Wegen der ausgezeichneten Stabilität der erfindungsgemäßen Dispersionen ist es ohne weiteres möglich, Lösungsmittel oder flüchtige Restmonomere durch Entgasen in üblichen Destillationsapparaturen wie z.B. Rotationsverdampfern oder Dünnschichtern zu entfernen, ohne daß wie bei üblichen bekannten Emulsionen von Perfluoralkylpolymerisaten Koagulation eintritt. Nach Entgasung werden geruchsfreie Dispersionen erhalten, die eine hohe Lagerstabilität aufweisen. Der Feststoffgehalt der erfindungsgemäßen Dispersionen liegt, in Abhängigkeit von der Konzentration der vorgelegten Polyurethan- dispersion und der Menge des mit den Monomeren eingebrachten Wassers (und gegebenenfalls nicht entfernten Lösungsmittels), im allgemeinen bei 5 bis 50, vorzugsweise 10 bis 30 Gew.-%. Der Fluorgehalt im Feststoff liegt im allgemeinen bei 6 bis 50, vorzugsweise 10 bis 30 Gew.-%.The process according to the invention is generally at from 20 to 120 ° C., preferably from 50 to 100 ° C. temperatures if necessary carried out under an intergas atmosphere (nitrogen) and optionally under pressure, the monomers and the auxiliaries and additives being incorporated into the submitted polyurethane dispersion with constant mixing. Because of the excellent stability of the dispersions according to the invention, it is readily possible to remove solvents or volatile residual monomers by degassing in conventional distillation apparatuses, such as, for example, rotary evaporators or thin layers, without coagulation occurring as in the case of conventional known emulsions of perfluoroalkyl polymers. After degassing, odorless dispersions are obtained which have a long shelf life. The solids content of the dispersions according to the invention is generally 5 to 50, preferably 10 to 30,% by weight, depending on the concentration of the polyurethane dispersion provided and the amount of water (and, if appropriate, solvent not removed) introduced with the monomers. The fluorine content in the solid is generally 6 to 50, preferably 10 to 30,% by weight.
Aus den erfindungsgemäßen Dispersionen lassen sich Filme herstellen, die eine hervorragende Hydrophobie und Oleophobie aufweisen. Die Dispersionen sind hervorragend als Imprägniermittel geeignet, um Textilien aus natürlichen und synthetischen Fasern, Teppiche, Papier und Leder öl- und wasserabstoßend auszurüsten. Erfindungsgemäße Dispersionen, die blockierte Polyisocyanate in dispergierter Form enthalten, können durch kurzzeitiges Erhitzen der mit ihnen hergestellten Überzüge auf über 100°C liegende Temperaturen zu besonders hochwertigen vernetzten Beschichtungen verarbeitet werden.Films can be produced from the dispersions according to the invention which have excellent hydrophobicity and oleophobicity. The dispersions are excellent as impregnation agents to make textiles made of natural and synthetic fibers, carpets, paper and leather oil and water repellent. Dispersions according to the invention which contain blocked polyisocyanates in dispersed form can be processed into particularly high-quality crosslinked coatings by briefly heating the coatings produced with them to temperatures above 100.degree.
In den nachfolgenden Beispielen beziehen sich alle Prozentabgaben auf Gewichtsprozente.In the examples below, all percentages relate to percentages by weight.
In den nachfolgenden Beispielen werden folgende Polyurethandispersionen verwendet:The following polyurethane dispersions are used in the examples below:
Ansatz:
Aus dem bei 100°C im Vakuum entwässerten Polyester, dem N-Methylpyrrolidon, dem Trimethylolpropan, der Dimethylolpropionsäure und dem Triethylamin stellt man bei 60°C ein homogenes, klares Gemisch her. Dann gibt man das Diisocyanat zu und rührt ca. 2 Stunden bei 80°C, bis ein (korrigierter) NCO-Wert von 2,6 % erreicht ist.A homogeneous, clear mixture is produced at 60 ° C. from the polyester, which is dewatered at 100 ° C. in vacuo, the N-methylpyrrolidone, the trimethylolpropane, the dimethylolpropionic acid and the triethylamine. The diisocyanate is then added and the mixture is stirred at 80 ° C. for about 2 hours until a (corrected) NCO value of 2.6% is reached.
Man kühlt auf 60°C ab und gibt zu dem erhaltenen Prepolymer das Acetonazin zu. Unter gutem Rühren läßt man dann das Wasser zulaufen. Die sich bildende feinteilige Dispersion wird 5 Stunden bei 70°C nachgerührt. Der Feststoffgehalt beträgt 40 % und die Fordbecherviskosität (4 mm-Düse) 30 Sekunden.The mixture is cooled to 60 ° C. and the acetonazine is added to the prepolymer obtained. Allow to stir well then run in the water. The fine-particle dispersion that forms is stirred at 70 ° C. for 5 hours. The solids content is 40% and the Ford cup viscosity (4 mm nozzle) 30 seconds.
Ansatz:
Aus dem bei 100°C im Vakuum entwässerten Polyester, dem N-Methylpyrrolidon, der Dimethylolpropionsäure und dem Triethylamin stellt man bei 60°C ein homogenes, klares Gemisch her. Dann gibt man das Diisocyanat zu und rührt 2 bis 3 Stunden bei 80°C, bis ein (korrigierter)2) NCO-Wert von 2,3 % erreicht ist. Man kühlt auf 60°C ab und gibt zu dem erhaltenen Prepolymer nacheinander das blockierte Polyisocyanat 1) und das Acetonazin zu. Unter gutem Rühren läßt man dann das Wasser zulaufen, worauf sich eine feinteilige Dispersion bildet, die zuletzt 5 Stunden bei 70°C nachgerührt wird.A homogeneous, clear mixture is produced at 60 ° C. from the polyester, which is dewatered at 100 ° C. in vacuo, the N-methylpyrrolidone, the dimethylolpropionic acid and the triethylamine. The diisocyanate is then added and the mixture is stirred at 80 ° C. for 2 to 3 hours until a (corrected) 2) N CO value of 2.3% is reached. The mixture is cooled to 60 ° C. and the blocked polyisocyanate 1 ) and the acetonazine are added in succession to the prepolymer obtained. The water is then run in with thorough stirring, whereupon a finely divided dispersion forms, which is finally stirred at 70 ° C. for 5 hours.
Die so erhaltene Dispersion hat einen Feststoffgehalt von 40 % und eine Fordbecherviskosität (4 mm-Düse) von 18 Sekunden.
- 1) Das blockierte Polyisocyanat wird wie folgt hergestellt:
- Zu 1000 g einer 90 %igen Lösung eines durch Trimerisierung von Hexamethylendiisocyanat erhaltenen Isocyanurat - Polyisocyanats (NCO-Gehalt: 20,5 %, Lösungsmittel: Ethylglykolacetat) gibt man unter Kühlung 425 g Butanonoxim, verdünnt mit 345 g Ethylglykolacetat und läßt bei 60°C reagieren, bis im IR-Spektrum keine NCO-Bande (2250 cm-1) mehr nachweisbar ist. Das erhaltene blockierte Polyisocyanat liegt in Form einer 75 %igen Lösung vor.
- 2) Der bei der üblichen Amin-Säure-Titration gefundene NCO-Wert ist durch das im Prepolymer vorhandene Triethylamin verfälscht.
- 1) The blocked polyisocyanate is produced as follows:
- To 1000 g of a 90% solution of an isocyanurate polyisocyanate obtained by trimerization of hexamethylene diisocyanate (NCO content: 20.5%, solvent: ethyl glycol acetate) are added 425 g of butanone oxime with cooling, diluted with 345 g of ethyl glycol acetate and left at 60 ° C. react until no more NCO band (2250 cm-1) can be detected in the IR spectrum. The blocked polyisocyanate obtained is in the form of a 75% solution.
- 2) The NCO value found in the usual amine acid titration is falsified by the triethylamine present in the prepolymer.
Man bereitet folgende Lösungen bei 70°C:
- Lösung 1
- Lösung 2
- Solution 1
- Solution 2
Durch Mischen von Lösung 1 und 2 mit Hilfe eines Ultraschall-Dispergators bereitet man eine Monomeremulsion 3, die zur nachfolgenden Pfropfreaktion eingesetzt wird.A monomer emulsion 3 is prepared by mixing solutions 1 and 2 with the aid of an ultrasound disperser, which is used for the subsequent grafting reaction.
In einen Rührkolben gibt man als Vorlage 300 g Polyurethan-Dispersion A und erwärmt unter N2 auf 75°C. Bei 75°C dosiert man innerhalb 2 h gleichmäßig folgende Komponenten zu:
Anschließend rührt man 1 h bei 75°C nach, verdünnt mit 200 g entionisiertem Wasser und erhält eine stabile Dispersion ohne Feststoffausfall.The mixture is then stirred at 75 ° C. for 1 h, diluted with 200 g of deionized water and a stable dispersion is obtained without solid precipitation.
Zur Entgasung zieht man am Rotationsverdampfer bei 60°C und 200 mbar ca. 400 g Destillat ab. Man erhält als Rückstand 800 g einer stabilen, fast geruchsfreien Dispersion mit folgenden Analysendaten:
Man bereitet folgende Lösungen bei 70°CThe following solutions are prepared at 70 ° C
Durch Mischen von Lösung 1 und 2 mit Hilfe eines schnell laufenden Mischers bereitet man eine Monomeremulsion 3, die zur folgenden Pfropfreaktion eingesetzt wird:A monomer emulsion 3 is prepared by mixing solutions 1 and 2 using a high-speed mixer, which is used for the following grafting reaction:
In einen Rührkolben gibt man als Vorlage 300 g Polyurethan-Dispersion B und erwärmt unter N2 auf 75°C. Bei 75°C dosiert man innerhalb 2 h gleichmäßig 600 g Monomeremulsion 3, sowie eine Lösung von 5,0 g Dilauroylperoxid in 100 g Methylisobutylketon zu. Anschließend rührt man 1 h bei 75°C nach, verdünnt mit 400 g entionisiertem Wasser und erhält eine stabile Dispersion ohne Feststoffausfall.300 g of polyurethane dispersion B are introduced as a template into a stirred flask and heated to 75 ° C. under N 2 . At 75 ° C., 600 g of monomer emulsion 3 and a solution of 5.0 g of dilauroyl peroxide in 100 g of methyl isobutyl ketone are metered in uniformly over the course of 2 hours. The mixture is then stirred at 75 ° C. for 1 h, diluted with 400 g of deionized water and a stable dispersion is obtained without solid precipitation.
Die Dispersion kann am Rotationsverdampfer bei 60°C und 200 mbar unter Abziehen von ca. 400 g Destillat entgast werden. Man erhält 1000 g einer stabilen, fast geruchsfreien Dispersion mit folgenden Analysendaten:
Man bereitet folgende Lösungen bei 60°C:
- Lösung 1
- Lösung 2
- Solution 1
- Solution 2
Durch Mischen von Lösung 1 und 2 mit Hilfe eines Ultraschall-Dispergators bereitet man eine Monomemulsion 3, die zur nachfolgenden Pfropfreaktion eingesetzt wird.By mixing solutions 1 and 2 with the aid of an ultrasound disperser, a mono-emulsion 3 is prepared which is used for the subsequent grafting reaction.
In einem Rührkolben gibt man als Vorlage 300 g Polyurethan-Dispersion A und erwärmt unter N2 auf 75°C. Bei 75°C dosiert man innerhalb 2 h gleichmäßig 900 g Monomeremulsion 3, sowie eine Lösung von 6,0 g Dilauroylperoxid in 100 g Essigsäureethylester zu.300 g of polyurethane dispersion A are introduced into a stirred flask and heated to 75 ° C. under N 2 . 900 g of monomer emulsion 3 and a solution of 6.0 g of dilauroyl peroxide in 100 g of ethyl acetate are metered in uniformly at 75 ° C. in the course of 2 hours.
Man rührt 1 h bei 75°C nach, zieht 300 g Destillat am Rotationsverdampfer bei 60°C und 200 mbar unter Zugabe von 300 g entionisiertem Wasser ab und erhält 1200 g einer stabilen Dispersion mit folgenden Analysendaten:
Man bereitet folgende Lösungen bei 70°C:
- Lösung 1
- Lösung 2
- Solution 1
- Solution 2
Durch Mischen von Lösung 1 und 2 mit Hilfe eines Ultraschalldispergators bereitet man eine Monomeremulsion 3, die zur folgenden Pfropfreaktion eingesetzt wird:A monomer emulsion 3 is prepared by mixing solutions 1 and 2 using an ultrasound disperser, which is used for the following grafting reaction:
Man gibt in einen Rührkolben als Vorlage 300 g Polyurethan-Dispersion A und erwärmt unter N2 auf 75°C. Bei 75°C dosiert man innerhalb 3 h gleichmäßig 600 g Monomeremulsion 3, sowie eine Lösung von 6,0 g Dilauroylperoxid in 100 g Methylisobutylketon zu.300 g of polyurethane dispersion A are introduced into a stirred flask and heated to 75 ° C. under N 2 . At 75 ° C., 600 g of monomer emulsion 3 and a solution of 6.0 g of dilauroyl peroxide in 100 g of methyl isobutyl ketone are metered in uniformly over the course of 3 hours.
Man rührt 30 min bei 80°C nach, zieht 300 g Destillat am Rotationsverdampfer bei 60°C und 200 mbar unter gleichzeitiger Zugabe von 300 g entionisiertem Wasser ab und erhält 1000 g einer stabilen Dispersion mit folgenden Analysedaten:
Man bereitet folgende Lösungen bei 70°C:
- Lösung 1
- Lösung 2
- Solution 1
- Solution 2
Durch Mischen von Lösung 1 und 2 mit Hilfe eines Ultraschalldispergators bereitet man eine Monomerenemulsion 3, die zur folgenden Pfropfreaktion eingesetzt wird:Mixing solutions 1 and 2 with the aid of an ultrasound disperser produces a monomer emulsion 3 which is used for the following grafting reaction:
Man gibt in einen Rührkolben als Vorlage 300 g Polyurethan-Dispersion A und erwärmt unter N2 auf 75°C. Bei 75°C dosiert man inerhalb 3 h gleichmäßig 600 g Monomerenemulsion 3, sowie eine Lösung von 5,0 g Dilauroylperoxid in 80 g Methylisobutylketon zu.300 g of polyurethane dispersion A are introduced into a stirred flask and heated to 75 ° C. under N 2 . At 75 ° C., 600 g of monomer emulsion 3 and a solution of 5.0 g of dilauroyl peroxide in 80 g of methyl isobutyl ketone are metered in uniformly within 3 hours.
Man rührt 30 min bei 80°C nach, zieht 300 g Destillat am Rotationsverdampfer bei 60°C und 200 mbar unter gleichzeitiger Zugabe von 300 g entionisiertem Wasser ab und erhält 1000 g einer stabilen Dispersion mit folgenden Analysedaten:
Claims (6)
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DE3407362 | 1984-02-29 | ||
DE19843407362 DE3407362A1 (en) | 1984-02-29 | 1984-02-29 | AQUEOUS DISPERSIONS OF GRAFT POLYMERS OR COPOLYMERS, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A HYDROPHOBIC AND OLEOPHOBIC AGENT FOR TEXTILES |
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EP0156155B1 EP0156155B1 (en) | 1987-04-29 |
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EP85101728A Expired EP0156155B1 (en) | 1984-02-29 | 1985-02-16 | Aqueous dispersions of graft polymers or graft copolymers, their preparation process and their use as water and oil repellent compositions for textile materials |
Country Status (6)
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US (1) | US4636545A (en) |
EP (1) | EP0156155B1 (en) |
JP (1) | JPS60206813A (en) |
CA (1) | CA1228442A (en) |
DE (2) | DE3407362A1 (en) |
HU (1) | HUT38662A (en) |
Cited By (6)
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EP0273449A1 (en) * | 1986-12-30 | 1988-07-06 | AUSIMONT S.p.A. | Aqueous dispersions of fluorinated polyurethanes and their use for textile coatings |
EP0303876A1 (en) * | 1987-08-10 | 1989-02-22 | Dainichiseika Color & Chemicals Mfg. Co. Ltd. | Polyurethane emulsion, sheet-like porous material making use of the emulsion and production process of the material |
EP0452774A2 (en) * | 1990-04-20 | 1991-10-23 | Bayer Ag | Graft copolymers containing perfluoroalkyl groups |
EP0560161A1 (en) * | 1992-03-12 | 1993-09-15 | Bayer Ag | Composition and process for the treatment of textiles |
EP0814102A2 (en) * | 1996-06-21 | 1997-12-29 | Bayer Ag | Graft polymers from unsaturated monomers onto modified polyurea, their preparation process and use |
CN108467471A (en) * | 2018-04-04 | 2018-08-31 | 优美特(北京)环境材料科技股份公司 | A kind of hyper-branched aqueous polyurethane dispersion of pectination and its preparation and application |
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DE3712069A1 (en) * | 1987-04-09 | 1988-10-20 | Basf Ag | USE OF GRAFT POLYMERISATS BASED ON POLYESTERS, POLYESTERURETHANES AND POLYESTERAMIDES AS GRAYING INHIBITORS IN DETERGENTS |
DE3722005A1 (en) * | 1987-07-03 | 1989-01-12 | Herberts Gmbh | METHOD FOR PRODUCING A MULTI-LAYER COATING AND AQUEOUS AQUEOUS COATING AGENT THEREFOR |
DE3939341A1 (en) * | 1989-11-29 | 1991-06-06 | Bayer Ag | HYDROPHOBIC AND OLEOPHOBIC AGENTS |
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JPH0559669A (en) * | 1991-08-29 | 1993-03-09 | Teijin Ltd | Production of stain-proofing water-repellent fabric |
DK0608021T3 (en) * | 1993-01-21 | 1997-10-20 | Akzo Nobel Nv | Water dispersible hybrid polymer. |
US5652291A (en) * | 1995-07-14 | 1997-07-29 | Seiko Chemical Industries Co., Ltd. | Aqueous dispersion of urethane vinyl composite resin |
GB9519824D0 (en) * | 1995-09-29 | 1995-11-29 | Secr Defence | Fibre reactive polymers |
JP4000614B2 (en) * | 1997-02-10 | 2007-10-31 | 大日本インキ化学工業株式会社 | Durable aqueous resin composition, antifouling coating agent and releasable coating agent |
US6359030B1 (en) * | 1997-10-24 | 2002-03-19 | Daikin Industries, Ltd. | Aqueous resin dispersion composition |
DE19930066A1 (en) | 1999-06-30 | 2001-01-11 | Basf Coatings Ag | Color and / or effect multi-layer coating, process for their preparation and their use |
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DE10106567A1 (en) * | 2001-02-13 | 2002-08-22 | Basf Coatings Ag | Aqueous primary dispersion essentially or completely free of volatile organic substances, process for their preparation and their use |
DE10106566A1 (en) * | 2001-02-13 | 2002-08-22 | Basf Coatings Ag | Aqueous coating material substantially or completely free of volatile organic substances, process for its preparation and its use |
DE10126651A1 (en) * | 2001-06-01 | 2002-12-12 | Basf Coatings Ag | Use of copolymers with diphenylethylene units as emulsifiers for the production of powder slurry and coating powder for use in coating materials, adhesives and sealants, e.g. for painting cars |
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DE10208567A1 (en) * | 2002-02-27 | 2003-09-11 | Degussa Construction Chem Gmbh | Aqueous fluorine-modified polyurethane system for anti-graffiti and anti-soiling coatings |
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JPS57139585A (en) * | 1981-02-13 | 1982-08-28 | Kao Corp | Color concentrating agent |
JPS6030796B2 (en) * | 1980-07-29 | 1985-07-18 | 花王株式会社 | darkening agent |
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- 1984-02-29 DE DE19843407362 patent/DE3407362A1/en not_active Withdrawn
-
1985
- 1985-02-16 DE DE8585101728T patent/DE3560149D1/en not_active Expired
- 1985-02-16 EP EP85101728A patent/EP0156155B1/en not_active Expired
- 1985-02-18 CA CA000474570A patent/CA1228442A/en not_active Expired
- 1985-02-19 US US06/703,011 patent/US4636545A/en not_active Expired - Fee Related
- 1985-02-27 JP JP60036736A patent/JPS60206813A/en active Granted
- 1985-02-28 HU HU85750A patent/HUT38662A/en unknown
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US3068187A (en) * | 1959-08-10 | 1962-12-11 | Minnesota Mining & Mfg | Process for preparing block and graft copolymers of perfluoroalkyl monomer and resulting product |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0273449A1 (en) * | 1986-12-30 | 1988-07-06 | AUSIMONT S.p.A. | Aqueous dispersions of fluorinated polyurethanes and their use for textile coatings |
US4983666A (en) * | 1986-12-30 | 1991-01-08 | Ausimont S.P.A. | Aqueous dispersions of fluorinated polyurethanes and their use for textile coatings |
US5068135A (en) * | 1986-12-30 | 1991-11-26 | Ausimont S.P.A. | Aqueous dispersions of fluorinated polyurethanes and their use for textile coatings |
EP0303876A1 (en) * | 1987-08-10 | 1989-02-22 | Dainichiseika Color & Chemicals Mfg. Co. Ltd. | Polyurethane emulsion, sheet-like porous material making use of the emulsion and production process of the material |
EP0452774A2 (en) * | 1990-04-20 | 1991-10-23 | Bayer Ag | Graft copolymers containing perfluoroalkyl groups |
EP0452774A3 (en) * | 1990-04-20 | 1992-01-15 | Bayer Ag | Graft copolymers containing perfluoroalkyl groups |
US5115013A (en) * | 1990-04-20 | 1992-05-19 | Bayer Aktiengesellschaft | Graft copolymers containing perfluoroalkyl groups |
EP0560161A1 (en) * | 1992-03-12 | 1993-09-15 | Bayer Ag | Composition and process for the treatment of textiles |
US5372731A (en) * | 1992-03-12 | 1994-12-13 | Bayer Aktiengesellschaft | Composition and process for the finishing of textiles |
EP0814102A2 (en) * | 1996-06-21 | 1997-12-29 | Bayer Ag | Graft polymers from unsaturated monomers onto modified polyurea, their preparation process and use |
EP0814102A3 (en) * | 1996-06-21 | 1998-09-23 | Bayer Ag | Graft polymers from unsaturated monomers onto modified polyurea, their preparation process and use |
CN108467471A (en) * | 2018-04-04 | 2018-08-31 | 优美特(北京)环境材料科技股份公司 | A kind of hyper-branched aqueous polyurethane dispersion of pectination and its preparation and application |
Also Published As
Publication number | Publication date |
---|---|
DE3407362A1 (en) | 1985-08-29 |
CA1228442A (en) | 1987-10-20 |
JPH0457687B2 (en) | 1992-09-14 |
EP0156155B1 (en) | 1987-04-29 |
US4636545A (en) | 1987-01-13 |
HUT38662A (en) | 1986-06-30 |
JPS60206813A (en) | 1985-10-18 |
DE3560149D1 (en) | 1987-06-04 |
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